Application of palladium catalyses to a simple synthesis of (±)-pyrethrolone

Tsuji, Jiro; Yamakawa, Tomio; Mandai, Tadakatsu

doi:10.1016/s0040-4039(01)95513-3

Cited by 18 publications

(13 citation statements)

References 11 publications

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“…The 1 H-NMR signals for the directly coupled hydrogens were assigned from the HMQC spectrum and 1 H, 1 H-COSY showed three contiguous spin systems (C1-2-3-4(-15)-5-6, C11(-13)-12 and C8-9, Figure 1A). [15] Pd-catalyzed hydrogenolysis [16] their identity.Acompound with identical spectroscopic data but incompletely assigned configuration was reported from the soft coral Nephthea chabrollii. Thering closure from C1 to C5 was evident from cross-peaks between H2 and C5 and between H6 and C1, resulting in the planar structure of guaia-6,10(14)-diene (1).…”

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confidence: 99%

Mechanistic Characterisation of Two Sesquiterpene Cyclases from the Plant Pathogenic Fungus Fusarium fujikuroi

et al. 2016

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Two sesquiterpene cyclases from Fusarium fujikuroi were expressed in Escherichia coli and purified. The first enzyme was inactive because of a critical mutation, but activity was restored by sequence correction through site-directed mutagenesis. The mutated enzyme and two naturally functional homologues from other fusaria converted farnesyl diphosphate into guaia-6,10(14)-diene. The second enzyme produced eremophilene. The absolute configuration of guaia-6,10(14)-diene was elucidated by enantioselective synthesis, while that of eremophilene was evident from the sign of its optical rotation and is opposite to that in plants but the same as in Sorangium cellulosum. The mechanisms of both terpene cyclases were studied with various (13) C- and (2) H-labelled FPP isotopomers.

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confidence: 99%

Mechanistic Characterisation of Two Sesquiterpene Cyclases from the Plant Pathogenic Fungus Fusarium fujikuroi

et al. 2016

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“…Synthesis of the rethrolone scaffold has been relatively universal in the syntheses of pyrethrolone to date, making use of the intramolecular aldol condensation of 1,4-diketones. 6,[9][10][11] As such, the original procedure by Matsuo and co-workers was initially used for this essential step of the pathway. Diketone 6 was added dropwise to a cooled, biphasic mixture of aqueous sodium hydroxide and toluene, and left to stir for 5 h. Following work-up, the crude mixture was shown to contain the desired rethrolone product 7 however, significant quantities of rethrolone dimers (16 and 17) were also present (Scheme 5) as indicated by the presence of alkene proton resonances and additional signals attributable to multiple propargyl side chains in the 1 H NMR analysis.…”

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confidence: 99%

A modified synthesis of (Z)-pyrethrolone

Johnston¹,

Markham²,

Duggan³

2022

Arkivoc

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An accessible, efficient, and reliable synthesis for the production of (Z)-pyrethrolone remains necessary as previous syntheses suffer from drawbacks including the use of toxic reagents, expensive starting materials and lack of regioselectivity in the production of key intermediates. This work attempts to alleviate the issues of prior syntheses by making use of well-known and regioselective transformations for the efficient synthesis of (Z)-pyrethrolone. Ultimately, (Z)-pyrethrolone is generated in an overall 20% yield over five steps from a cheap, easily accessible starting material using reliable, optimised transformations.

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“…Perfluoroalkylsulfonates as linkers to a solid-phase cleavable by palladium-catalyzed deoxygenation. [18] Their alkoxyalkyl ethers [methoxymethyl (MOM) or ethoxyethyl (EE)] can be deoxygenated selectively in the presence of other ethers, as exemplified in the synthesis of lavendulol Scheme 4. [16] This procedure was even found to deoxygenate stabilized triflates, whereas other reducible functional groups such as esters, aldehydes, nitro or bromo groups, and olefins were unaffected (Scheme 4).…”

Section: Palladium-catalyzed Deoxygenationsmentioning

confidence: 99%

“…[17] Besides phenolic hydroxy groups, allylic alcohols can also be deoxygenated catalytically with palladium. [18] Their alkoxyalkyl ethers [methoxymethyl (MOM) or ethoxyethyl (EE)] can be deoxygenated selectively in the presence of other ethers, as exemplified in the synthesis of lavendulol Scheme 4. Aryl and vinyl triflates deoxygenated by homogeneous palladium catalysis.…”

Section: Palladium-catalyzed Deoxygenationsmentioning

confidence: 99%

Reductive Deoxygenation of Alcohols: Catalytic Methods Beyond Barton–McCombie Deoxygenation

2013

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Deoxygenation is an extensively studied field in organic chemistry, and over the last decades many methods such as the Barton–McCombie deoxygenation reaction or deoxygenation with alkali metals in liquid ammonia have been established. Within this microreview, we discuss different strategies for the chemoselective catalytic deoxygenation of alcohols with special attention to their scope and limitations. The deoxygenation of derivatives of alcohols and their direct deoxygenation as step‐economic alternative are covered with current examples. Catalytic methods can serve as convenient and economic alternatives for established methods in the reduction of carbon–oxygen single bonds.

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Application of palladium catalyses to a simple synthesis of (±)-pyrethrolone

Cited by 18 publications

References 11 publications

Mechanistic Characterisation of Two Sesquiterpene Cyclases from the Plant Pathogenic Fungus Fusarium fujikuroi

Mechanistic Characterisation of Two Sesquiterpene Cyclases from the Plant Pathogenic Fungus Fusarium fujikuroi

A modified synthesis of (Z)-pyrethrolone

Reductive Deoxygenation of Alcohols: Catalytic Methods Beyond Barton–McCombie Deoxygenation

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